US2172308A - Process for the production of light-sensitive materials for color photographic purposes - Google Patents

Process for the production of light-sensitive materials for color photographic purposes Download PDF

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US2172308A
US2172308A US190878A US19087838A US2172308A US 2172308 A US2172308 A US 2172308A US 190878 A US190878 A US 190878A US 19087838 A US19087838 A US 19087838A US 2172308 A US2172308 A US 2172308A
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component
derivative
soluble
insoluble
emulsion
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US190878A
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Gaspar Bela
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/388—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor

Definitions

  • the present invention relates to a process of producing photographic materials for color photographic purposes which enables insoluble or diflicultly soluble dyestufi components to be incorporated in the photographic colloid in a very simple and reliable manner.
  • the process consists in incorporating the desired dyestuif component in the colloid not in the form of the component itself but in the form of a soluble. de-
  • dyestufl component any substance capable of forming a'dyestuff by reacting or coupling with a second dyestufi component, if necessary after a.
  • pretreatment such as, for instance, diazotizing.
  • the soluble derivative is preferably one that is derived from an organic dyestufi component hav-' ing an at least bi-valent inorganic atom linkedto 2a a carbon atom of the molecule and a radical imparting a salt-forming character hydrolysably linked with the said inorganic atom in which case the splitting oif of the component is effected by hydrolysis. More particularly, the bisulfite and aldehyde bisulfite addition products of a20- dyestufl components, the w-SlllDhOlliO acid salts of the amino compounds and the sulphaminic acid salts derived from tlitlyestufl forming substances containing an amino for carrying out this process.
  • the process of producing light-sensitive'materials according to the present invention therefore, consists in" incd'rporating into the solutions: employed for the production of the emulsion, into the emulsion itself or into the finished lightsensitive layer, s'o'lubfe derivatives of insoluble or difilcultly soluble dye'stufi components, the 'said derivatives being split up to give the-dyestuif components to be employed in the production of the colored image prior to exposure of the, material;
  • the present invention is generally applicable to dyestuil' components in the light-sensitive material whatever be the method subsequently employed for the production of they colored image.
  • group a are suitable theincorporation of insoluble or diflicultly soluble both of which the advantage of using insoluble or diflicultly soluble dyestufl. components 'is stressed.
  • water-insoluble dyestufl components have been ,incorporatedinto the materials 5 as such, for example, by dissolving them in alcohol and mixing the alcoholic solution with the gelatine solution.
  • salt forming dyestuif components- were used inthe form of water-soluble alkali-salts from which the dye- 10 stufi component was precipitated.
  • the first ot these methods has the disadvantage that upon mixing the alcoholic solution with the gelatine an immediate precipitation of the dyestufl components takes place, this giving a much more un- 15 even precipitation than the process of the present invention, in which precipitation is only. brought about after the dyestufi component has become evenly distributed throughout the whole of the emulsion or the gelatine employedior the 20 production of the photographic colloid.
  • tives of the dyestufl components used in carrying out thepresent invention are substitution products which cannot be reconverted into the soluble deriyativeiafter they have once been'split up within the layer. Accordingly they may, if 30 necessary, be so chosen that they are not dissolved in the developer.
  • the splitting .up of the soluble derivative in carrying out the present invention Isis. comparatively slow reaction which extends throughout 35 the whole'of the emulsion and/or colloid and consequently the insoluble or difflcultly soluble component is produced in a state of very fine subdivision.
  • insoluble or diflicultly 40 soluble dyestufi components used herein are included not only those dyestuff components which are practically insoluble in water or the emulsion 'but alsothose dyestuff components, the solubility of which is insufiicient to enable a sufliclent 45 quantity for practical use to be dissolved in the emulsion. If, for example, a dyestufl' component is soluble in water to the extent of one part in one hundred, then only one-half per cent of the component can be introduced into the emulsion by mixing equal quantities of the solution and the emulsion. The use of a larger amount 01' Water to increase the amount of dyestufr present results in a dilution of the emulsion which is,a,
  • the light-sensitive materials according to the presentinvention contain the dyestuii' components, after splitting up, in an extremely finely divided state whereby they, despite their insolubility, readily react with the subsequently applied reagents to' produce an intense dyeing of the layer.
  • the dyestuif may be produced diffusely throughout the layer or locally at the image or non-image parts thereof accordponents.
  • Benzidine is used in the form of the sodium salt of the benzidine-N-N'-dimethyl-w'-disulphonic acid (see Bucherer- 8r Schwalbe, Berichte de Deutschen Chemischn Deutschen, 1906 volume 39, page 2805).
  • This derivative is incorporated in the gelatine which is to be used for preparingthe emulsion or which is to be added to the light- 5 sensitive emulsion, and the gelatine is then treated with a weak solution (say 1%) of ammonia, sodium carbonate or other alkali.
  • the gelatine in allowed to stand at a temperature of about 40 C. in order that the splitting up may be completed. It is then coagulated, brought into noodleform, washed and after re-melting is mixed with the light-sensitive emulsion.
  • benzidine in place of benzidine, other amines such as p-naphthylamine, tolidine or dianisidine may be used in the form of the N-methyl-u-sulphonic acid salts or the homologues obtained, for example, from acetaldehyde-bisulfite or benzaldehyde-bisulflte compounds.
  • the amines may also be used in the form of sulphaminic acid salts of which naphthylamine sulphaminic acid (Berichte volume 24 pages 360 and 363) may be cited as an example. Such a derivative is split up by means of diluted acid.
  • Phenol may be used in the form of a phenylsulphonic acid salt such as CsHsO.SO:Na (Verley,
  • Naphthol may alsobe used in the form' of the naphthyl sulphonic acid salt and similarly a-dinaphthol in the form of the corresponding sulphonic acid ester.
  • esters that these phenols form with bi-valent organic acids may also be used.
  • the salts of such esters have the formula, for example,
  • Dyestufl components of the aceto-acetic ester type may be used in the form of their bisulfite compounds.
  • the isoamyl ester of aceto-acetic acid is dimcultly soluble, whilst its bisulfite compounds, which are capable of being split up as herein described, are readily soluble.
  • Such bisulfite compounds may be prepared in an analogous manner to the preparation of the bisulfite compound of the aceto-acetic ester described by Ellen, Recueil des Travaux Chimiques des Pays-Bas, volume 3, page 245.
  • 5 Aldehydes may also be used as the dyestuif components.
  • 3-nitrobenzaldehyde may be used in the form of its bisulfite compound. The aldehyde yields a red-yellow dyestuil' with 'di-hydrazine-stilbene-disulphonic [0 acid after the splitting up.
  • a dyestuif component which itself has a fairly high solubility in water go but which, in order to reduce the aqueous dilution, is'used in the form of a still more easily soluble derivative in order that it may be introduced in a higher concentration into the photographic colloid.
  • the di- 35 methyl-di-omega-sulphonic acid sodium saltof Diazo light yellow (Fierz-David 1926 page 154) is used instead of the Diazo light yellow itself.
  • This salt is formed in a mannersimilar to that of the corresponding benzidine salt above referred to 30. and is split up in the emulsion prior to exposure.
  • the splitting up of the soluble derivatives of the insoluble. or dimcultl'y soluble dyestufi components is carried out in the presence 35 of a precipitating agent that yields an insoluble and non-diffusing salt of the dyestufi' component set free on the splitting up.
  • a precipitating agent that yields an insoluble and non-diffusing salt of the dyestufi' component set free on the splitting up.
  • Suitable precipitating agents are, for example, di-phenyl guanidine and. quaternary naphthoquinolinium salts.
  • the splitting up of the soluble deriva-.- tives of the dyestufl components is effected in the presence of wetting agents and emulsifying agents.
  • the use of such agents produces an especially fine dispersion of the dyestufi' com- 50' ponents.
  • Suitable agents for use in carrying out this feature of the present invention are, for example, soap derived from sulphonated castoroil (known in Germany as Monopolselfe) fatty acid sulphinates, salts of cholic acid, lignon-sulphonic 6i
  • the method of the introduction of the dyestufl 08' components will be described by way of anexample showing in what manner a component is incorporated into the light-sensitive emulsion' using its formaldehyde bisulfite compound. 5 g. of the formaldehyde bisulfite compound of to an amine is dissolved in 50 com. water at about C. 50 com. of a gelatine solution of 20% strength are added with stirring and also 5 com.
  • the emulsion so prepared is then poured upon a glass plate or upon another support.
  • chloro-sulphonic acid are used and the solution of the dinaphtol is slowly added to the solution of the chloro-sulphonic' acid; then the mixture is heated for 5 hours on the water bath; after this the pyridine'is distilled oil in vacuo and then the remainder is dissolved in an aqueous sodium acetate solution of 27.2% strength out of which the compound crystallizes in long needles on cooling. 0.1 g. oi!
  • the gelatine is mixed with a light sensitive emulsion poured on to a glass plate and is converted into dyer layers aftertheexposure and developing with diazo solutions; from these layers the dyestufi can be removed locally in the known manner for the production of dyestufl images.
  • the invention does not limit itself to the use of the substances given as examples, but can also he used in order to introduce other dyestuif components, as for example diphenylamin, in the form of its, soluble scisslble compounds, for ex-- ample the formaldehyde bisulfite' compound, into the gelatine or the emulsion and from this to set free the component before the exposure.
  • the principle of the new process is based on the fact that an insoluble or difiicultly soluble dyestuijf component is incorporated into the layer in such a' way that one of its derivatives is produced which contains a radical which can be split oil againl-athis i'adie cal makes the component soluble; before the exposure, the soluble derivative is split up into the original component which then remains in .the
  • the radical which can be split oi! consists of a salt-forming group which is linked to the dyestuiI component by a hydrolysable linkage.
  • an inorganic atom forming a. part of the component such as for instance the oxygen atom 01' a phenolic component or a nitrogen atom of an amino or iminocompound brings about the union with the radical which can be split OH to form again the phenol or the amino compound.
  • a process oi producing photographic materials which includes incorporating a soluble hydrolyzable derivative oi an insoluble azo-dye component into a colloid used for the formation of a layer of said photographic material, said azo-dye component havingan inorganic atom selected from the group consisting of oxygen and nitrogen linked to a carbon atom of the molecule and said derivative having an acid salt-forming radical linked in hydroiyzable linkage to said inorganic atom, the step which consists in treating said colloid and said derivative, simultaneously and prior to exposure by a hydrolyzing agent which does not adversely afiect said colloid.
  • a process of producing photographic materials which includes incorporating a soluble irvdrolyzable derivative of an insolubleazo-dye component into a colloid used for the formation of a-layer oi said photographic material, said azo-dye component having an inorganic atom selected from the group consisting of oxygen and nitrogen linked to a carbon atom of the molecule and said derivative havingan acid salt-forming radical linked in hydrolyzable linkage to said inorganic atom, the step which consists in treating said coloid and said derivative, simultaneously and prior to exposure and in the presence oi a wetting agent by a hydrolyzing' agent which does not adversely aflect said colloid.
  • organic atom selected from the group consisting of oxygen and nitrogen linked to a carbon atom of the molecule and said derivative of the component having anacid salt-forming radical in hydrolyzabie linkage with said inorganic atom, splitting off the dyestufl component from the dissolved derivative within the gelatin solution by a hydrolyzing agent which does not adversely affect said gelatine solution, mixing the gelatin with silver halide, pouring said emulsion onto the support, exposing the light sensitive layer, developing the silver image, transforming the dyestufi component into an azo dyestui! and destroying the azo dyestuii locally-in proportion to the silver deposit.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US190878A 1937-02-20 1938-02-16 Process for the production of light-sensitive materials for color photographic purposes Expired - Lifetime US2172308A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2425503A (en) * 1944-05-20 1947-08-12 Gen Aniline & Film Corp Nondiffusing couplers for color photography
US2430845A (en) * 1942-12-09 1947-11-11 Du Pont Cyanine dyes containing a sulfamate anion
US2500080A (en) * 1945-02-02 1950-03-07 Francolor Sa Insolubilization of a soluble azoic dyestuff on the fiber
US2704710A (en) * 1950-04-18 1955-03-22 Gen Aniline & Film Corp Precipitation of azo dyes in silver halide emulsions by means of guanidine and biguanide compounds containing long alkyl chains

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2699394A (en) * 1950-12-15 1955-01-11 Gaspar Bela Production of photographic dye images

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2430845A (en) * 1942-12-09 1947-11-11 Du Pont Cyanine dyes containing a sulfamate anion
US2425503A (en) * 1944-05-20 1947-08-12 Gen Aniline & Film Corp Nondiffusing couplers for color photography
US2500080A (en) * 1945-02-02 1950-03-07 Francolor Sa Insolubilization of a soluble azoic dyestuff on the fiber
US2704710A (en) * 1950-04-18 1955-03-22 Gen Aniline & Film Corp Precipitation of azo dyes in silver halide emulsions by means of guanidine and biguanide compounds containing long alkyl chains

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GB510884A (en) 1939-08-09

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